KR20210015824A - Moisture-curable polyolefin formulation - Google Patents

Abstract

It relates to a moisture-curable preparation comprising a (hydrolyzable silyl group)-functional polyolefin prepolymer and an ascorbyl carboxylate ester. It relates to methods of making and using the same, cured polyolefins made therefrom, and articles containing or made from them.

Description

Moisture-curable polyolefin formulation

Moisture-curable formulations comprising moisture-curable polyolefins and ascorbic carboxylic acid esters, methods of making and using the same, cured polyolefins made therefrom, and articles containing or made from the same.

Publication of a patent application pertaining to or relating to the technical field is provided in CA 2161991A1; CN105754185A; CN 105949547A; EP 2 889 323 A1; US 2003/0109494 A1; US 2008/0176981 A1; US 2010/0056809 A1; US 2011/0282024 A1; US 2015/0166708 A1; US 2016/0200843 A1; WO 2000/071094 A1 and WO 2005/110123 A1. Patents in this technical field are disclosed in US 5,686,546; US 6,162,419; US 6,936,655 B2; And US 9,790,307 B2.

The inventors have found that ascorbyl carboxylate esters are useful as metal-free, environmentally stable non-toxic catalysts that improve the curing of moisture-curable polyolefins. The technical solution of the present inventors includes a moisture-curable preparation comprising a (hydrolyzable silyl group)-functional polyolefin prepolymer and an ascorbyl carboxylate ester. The technical solutions also include methods of their manufacture and use, cured polyolefins made therefrom, and articles containing or made from them.

The content and summary of the invention is incorporated herein by reference. Examples of embodiments include the following numbered aspects.

(I)의 아스코르빌 카르복실레이트 에스테르를 포함하는 수분-경화성 제제로서, 상기 식에서, R은 비치환된 (C₁-C₄₅)하이드로카르빌기이고; 상기 (A)는 (A)와 (B)의 합산 중량의 89.0 내지 99.9 중량 퍼센트(wt%)이고, (B)는 (A)와 (B)의 합산 중량의 11.0 내지 0.1 wt%이며; 상기 (A)는 수분-경화성 제제의 총 중량의 40 내지 99.9 wt%이고, 상기 (B)는 수분-경화성 제제의 총 중량의 0.1 내지 11 wt%인, 수분-경화성 제제. "비치환된(unsubstituted)"은, R이 탄소 및 수소 원자로 이루어진다는 것을 의미한다. R은 (C₁-C₄₅)알킬기, (C₂-C₄₅)알케닐기, (C₆-C₁₂)아릴기, (C₁-C₂₅)알킬-치환된 (C₆-C₁₂)아릴기, 또는 (C₆-C₁₂)아릴-치환된 (C₁-C₂₅)알킬기일 수 있다.Aspect 1.(A) (hydrolyzable silyl group)-functional polyolefin prepolymer and (B) formula (I):

A moisture-curable preparation comprising the ascorbyl carboxylate ester of (I), wherein R is an unsubstituted (C ₁ -C ₄₅ )hydrocarbyl group; (A) is 89.0 to 99.9 wt% (wt%) of the combined weight of (A) and (B), and (B) is 11.0 to 0.1 wt% of the combined weight of (A) and (B); The (A) is 40 to 99.9 wt% of the total weight of the moisture-curable formulation, and (B) is 0.1 to 11 wt% of the total weight of the moisture-curable formulation, the moisture-curable formulation. “Unsubstituted” means that R consists of carbon and hydrogen atoms. R is (C ₁ -C ₄₅ )alkyl group, (C ₂ -C ₄₅ )alkenyl group, (C ₆ -C ₁₂ )aryl group, (C ₁ -C ₂₅ )alkyl-substituted (C ₆ -C ₁₂ )aryl Group, or (C ₆ -C ₁₂ ) aryl-substituted (C ₁ -C ₂₅ ) alkyl group.

Aspect 2. In aspect 1, the (A) (hydrolyzable silyl group)-functional polyolefin prepolymer is characterized by any one of limitations (i) to (iii): (i) each hydrolyzable silyl group is independently Formula (II): (R ² ) _m (R ³ ) _3-m Si- (II) is a monovalent group; In the above formula, the subscript m is an integer of 1, 2 or 3; Each R ² is independently H, HO-, (C ₁ -C ₆ )alkoxy, (C ₂ -C ₆ )carboxy, ((C ₁ -C ₆ )alkyl) ₂ N-, (C ₁ -C ₆ )Alkyl(H)C=NO-, or ((C ₁ -C ₆ )alkyl) ₂ C=NO-; Each R ³ is independently (C ₁ -C ₆ )alkyl or phenyl; (ii) the polyolefin moiety of (A) is polyethylene-based, poly(ethylene- co- (C ₃ -C ₄₀ )alpha-olefin)-based, or a combination thereof; (iii) a moisture-curable formulation, which is both (i) and (ii).

Aspect 3. In aspect 1 or aspect 2, the (B) ascorbyl carboxylate ester of formula (I) is characterized by any one of restrictions (i) to (xviii), wherein: (i) R is ( C ₁ -C ₄₅ )alkyl group; (ii) R is a branched (C ₁ -C ₄₅ )alkyl group; (iii) R is a linear (C ₁ -C ₄₅ )alkyl group; (iv) R is an unsubstituted linear (C ₁ -C ₄₅ )alkyl group; (v) R is a (C ₁ -C ₃₅ )alkyl group; (vi) R is a (C ₁ -C ₂₅ )alkyl group; (vii) R is a (C ₉ -C ₂₅ )alkyl group; (viii) R is a (C ₁₁ -C ₁₉ )alkyl group; (ix) R is a (C ₁₂ -C ₁₈ )alkyl group; (x) R is a (C ₁₃ -C ₁₇ )alkyl group; (xi) R is a (C ₁₄ -C ₁₆ )alkyl group; (xii) R is a linear (C ₁₄ -C ₁₆ )alkyl group; (xiii) R is a (C ₁₄ )alkyl group; (xiv) R is a linear (C ₁₄ ) alkyl group; (xv) R is a (C ₁₅ )alkyl group; (xvi) R is a linear (C ₁₅ )alkyl group; (xvii) R is a (C ₁₆ )alkyl group; (xviii) R is a straight chain (C ₁₆ ) alkyl group, a moisture-curable preparation.

Aspect 4. In aspect 1 or 2, wherein (B) the ascorbyl carboxylate ester of formula (I) is characterized by any one of restrictions (i) to (v): (i) R is (C ₂ -C ₄₅ ) alkenyl group, (C ₆ -C ₁₂ ) aryl group, (C ₁ -C ₂₅ ) alkyl-substituted (C ₆ -C ₁₂ ) aryl group, or (C ₆ -C ₁₂ ) aryl-substituted Is a (C ₁ -C ₂₅ )alkyl group; (ii) R is a (C ₂ -C ₄₅ )alkenyl group; (iii) R is a (C ₆ -C ₁₂ )aryl group; (iv) R is a (C ₁ -C ₂₅ )alkyl-substituted (C ₆ -C ₁₂ )aryl group; (v) R is a (C ₆ -C ₁₂ ) aryl-substituted (C ₁ -C ₂₅ ) alkyl group, a moisture-curable agent.

Aspect 5. (B ^Ox ) reaction product of the oxidation of (B) ascorbyl carboxylate ester with (C) peroxide and/or (C) peroxide according to any one of aspects 1 to 4 But additionally include; The (C) peroxide is (C1) hydrocarbyl hydroperoxide or (C2) an organic peroxide, a moisture-curable preparation. In some embodiments, the (C) peroxide is (C1), and the (C1) is cumyl hydroperoxide.

Aspect 6. The moisture-curable agent according to any one of aspects 1 to 5, further comprising at least one additive selected from additives (D) to (I): (D) a flame retardant; (E) antioxidants; (F) metal deactivating agents (eg, oxalyl bis(benzylidene)hydrazide (OABH)); (G) colorants; (H) moisture remover; And (I) a combination of any two or more of (D) to (H).

(I)의 아스코르빌 카르복실레이트 에스테르를 혼합하여 혼합물을 제공하되, 상기 식에서, R은 (C₁-C₄₅)알킬기인 단계; 및 상기 혼합물을 용융 또는 압출시켜, 수분-경화성 제제를 제조하는 단계를 포함하는, 방법. 상기 방법에 의해 제조된 수분-경화성 제제는, 양태 1 내지 6 중 어느 하나의 것일 수 있다.Embodiment 7. A method for preparing a moisture-curable formulation, the method comprising (A) (hydrolyzable silyl group)-functional polyolefin prepolymer and (B) formula (I):

Mixing the ascorbyl carboxylate ester of (I) to provide a mixture, wherein R is a (C ₁ -C ₄₅ )alkyl group; And melting or extruding the mixture to produce a moisture-curable formulation. The moisture-curable preparation prepared by the above method may be any one of Aspects 1 to 6.

Aspect 8. To provide a moisture-cured polyolefin product, the moisture-curable agent of any one of aspects 1 to 6, or a product obtained by moisture-curing the moisture-curable agent prepared by the method of aspect 7 Cured polyolefin product.

Aspect 9. An article of manufacture comprising a molded form of the moisture-cured polyolefin product of aspect 8.

Aspect 10. A coated conductor comprising a conductive core and a polymer layer at least partially surrounding the conductive core, wherein at least a portion of the polymer layer comprises the moisture-cured polyolefin product of aspect 8.

Aspect 11. A method of conducting electricity, the method comprising applying a voltage to a conductive core of the coated conductor of aspect 10 to generate a flow of electricity through the conductive core.

Moisture-curable formulation. The total weight of all constituents in the moisture-curable formulation is 100.00 wt%. The moisture-curable preparation may further contain water.

The moisture-curable polyolefin composition may be a one-part formulation, alternatively a multi-part formulation, such as a two-part formulation. The two-part formulation may comprise a first part and a second part, wherein the first part consists essentially of (A) (hydrolyzable silyl group)-functional polyolefin prepolymer and (B) ascorbyl carboxylate ester. And, the second part basically consists of an additional part of (A) and optionally any one or more of the constituent components (C) to (H).

Moisture-curable formulations may be in continuous (monolithic) or divided solid form. Moisture-curable formulations may include granules and/or pellets. Prior to the mixing step used in the preparation of the moisture-curable preparation, the (A) (hydrolyzable silyl group)-functional polyolefin prepolymer may also be in divided solid form (eg granules or pellets).

In some embodiments, the moisture-curable agent does not include a carboxylic acid of formula R—CO ₂ H, or a salt thereof (eg, amine or metal salt).

Constituent component (A) (hydrolyzable silyl group)-functional polyolefin prepolymer ("(A) prepolymer"). (A) The polyolefin portion of the prepolymer may be polyethylene, which means that the (A) prepolymer has a skeleton formed by polymerization of ethylene. Alternatively, (A) the prepolymer may be a poly(ethylene- co- (C ₃ -C ₄₀ )alpha-olefin) system, which (A) the prepolymer is a skeleton formed by copolymerization of ethylene and at least one alpha-olefin Means to have.

(A) The prepolymer may be a reactant copolymer of ethylene and an alkenyl-functional hydrolyzable silane. The alkenyl-functional hydrolyzable silane may be of the formula (III) (R ² ) _m (R ³ ) _3-m Si-(C ₂ -C ₆ ) alkenyl (III), wherein m, R ² , and R ³ are as defined above for formula (II). (C ₂ -C ₆ )Alkenyl may be vinyl, allyl, 3-butenyl, or 5-hexenyl. In some embodiments, the (A) prepolymer is a reactive copolymer of ethylene and vinyltrimethoxysilane. Vinyltrimethoxysilane is an example of an alkenyl-functional hydrolysable silane of formula (III), wherein the subscript m is 3, and each R ² is (C ₁ -C ₆ )alkoxy, especially methoxy ego; (C ₂ -C ₆ )Alkenyl is vinyl (-C(H)=CH ₂ ).

Alternatively, the (A) prepolymer may be a reactor copolymer of ethylene, alpha-olefins, and alkenyl-functional hydrolysable silanes, for example in US 6,936,671.

Alternatively, (A) the prepolymer is a homopolymer of ethylene having a carbon atom skeleton having a hydrolyzable silyl group grafted thereto, such as a hydrolyzable unsaturated silane (e.g., vinyltrimethoxy Silane), but usually catalyzed by a free radical initiator such as dialkyl peroxide, and separating the resulting silane-grafted polymer (e.g., SIOPLAS™ Process). The grafted polymer can be used in a subsequent fabricating step.

Alternatively, the (A) prepolymer may be a copolymer of ethylene and at least one of (C ₃ -C ₄₀ )alpha-olefins and unsaturated carboxylic esters (e.g., (meth)acrylate alkyl esters), The copolymer has a skeleton having a hydrolyzable silyl group grafted thereto, and is prepared, for example, by the SIOPLAS™ process.

Alternatively, (A) the prepolymer may be a mixture of ethylene, a hydrolyzable silane, such as an alkenyl-functional hydrolyzable silane of formula (III), and a peroxide, which is prepared after polymerization or in an extrusion step. Reactively grafting a silane (e.g. vinyltrimethoxysilane), but usually catalyzed by a free radical initiator such as dialkyl peroxide, and the resulting silane-grafted polymer in a later processing step It is suitable for use in processes involving immediate (without separation) use steps (eg, MONOSIL™ processes).

Alternatively, (A) the prepolymer is a copolymer of ethylene and at least one of (C ₃ -C ₄₀ )alpha-olefins and unsaturated carboxylic esters, hydrolysable silanes, such as alkenyl-functional hydrolysable of formula (III). It may be a mixture of silane, and peroxide, which is suitable for SIOPLAS™ or MONOSIL™ processes. The alpha-olefin may be (C ₃ -C ₄₀ )alpha-olefin, alternatively (C ₃ -C ₂₀ )alpha-olefin, alternatively (C ₃ -C ₁₀ )alpha-olefin. The alpha-olefin may have at least 4 carbon atoms (ie, it may be (C ₄ )alpha-olefin or greater). Examples of (C ₃ -C ₁₀ ) alpha-olefins are propylene, 1-butene, 1-hexene, 1-octene, and 1-decene. The peroxide may be an organic peroxide, such as described in line 6 of page 5 to line 2 of page 6 of WO 2015/149634 A1, or (C1) as described below for organic peroxide.

Alternatively, (A) (hydrolyzable silyl group)-functional polyolefin prepolymer ("(A) prepolymer") comprises: (i) a reactor copolymer of ethylene and a hydrolyzable silane; (ii) reactive copolymers of ethylene, hydrolysable silanes, and one or more alpha-olefins and unsaturated carboxylic acid esters (eg, US 6,936,671); (iii) a homopolymer of ethylene having a carbon skeleton and a hydrolyzable silane grafted to the carbon skeleton (for example, prepared by the SILOPAS™ process); (iv) Copolymer of ethylene, at least one alpha-olefin and unsaturated carboxylic acid ester, having a backbone and hydrolysable silanes grafted to the backbone (for example, prepared by the SILOPAS™ process). ; (v) copolymers formed from mixtures of ethylene, hydrolysable silanes, and organic peroxides (eg, prepared by the MONOSIL™ process); Or (vi) a copolymer formed from a mixture of ethylene, and one or more alpha-olefins and unsaturated carboxylic esters, hydrolysable silanes, and organic peroxides (eg, prepared by the MONOSIL™ process).

(A) The prepolymer is 89.0 to 99.95 weight percent (wt%), alternatively 94.0 to 99.95 wt%, alternatively 97.0 to 99.90 wt% of the combined weight of (A), (B), and optionally (C). to be.

(A) The prepolymer comprises in the moisture-curable formulation, all from 40 to 99.9 wt%, alternatively at least 50 wt%, alternatively at least 60 wt%, based on the total weight of the moisture-curable formulation; And alternatively at most 99 wt%, alternatively at most 95 wt%, alternatively at most 80 wt%.

(I)의 아스코르빌 카르복실레이트 에스테르이고, 상기 식에서, R은 비치환된 (C₁-C₄₅)하이드로카르빌기이다.Constituent component (B) Ascorbyl carboxylate ester. (B) is the formula (I):

(I) is the ascorbyl carboxylate ester, wherein R is an unsubstituted (C ₁ -C ₄₅ )hydrocarbyl group.

“Unsubstituted” means that R consists of carbon and hydrogen atoms. R is (C ₁ -C ₄₅ )alkyl group, (C ₂ -C ₄₅ )alkenyl group, (C ₆ -C ₁₂ )aryl group, (C ₁ -C ₂₅ )alkyl-substituted (C ₆ -C ₁₂ )aryl Group, or (C ₆ -C ₁₂ ) aryl-substituted (C ₁ -C ₂₅ ) alkyl group. In some embodiments, R is as defined above. In some embodiments, (B) the ascorbyl carboxylate ester of formula (I) is ascorbyl palmitate or ascorbyl stearate.

(1)의 1가 구조이고, 상기 식에서, O-는 가장 우측 O 상의 라디칼을 나타낸다. 일부 양태에서, (B)의 아스코르빌 부분은 라세미 상태이다. 다른 양태에서, (B)의 아스코르빌 부분은 입체화학적으로 특정 입체이성질체가 풍부하다. 일부 양태에서, (B)의 아스코르빌 부분은 D-아스코르브산으로부터 유도된다. 일부 양태에서, (B)의 아스코르빌 부분은 L-아스코르브산으로부터 유도된다. 일부 양태에서, (B)의 아스코르빌 부분은 L-아스코르브산으로부터 유도되고, 화학식 (I) 중의 R 기는 팔미트산으로부터 유도되어, (B)는 화학식 (I-a):

(I-a)의 화합물이다. 화학식 (I-a)의 화합물은 또한 이하의 명칭들 중 어느 하나로도 알려져 있다: 6-O-팔미토일-L-아스코르브산, L-아스코르브산 6-헥사데카노에이트, L-아스코르빌 팔미테이트, 및 아스코르브산 6-팔미테이트.The ascorbyl moiety of (B) is the formula (1):

It is the monovalent structure of (1), wherein O- represents a radical on the rightmost O. In some embodiments, the ascorbyl portion of (B) is in a racemic state. In another embodiment, the ascorbyl moiety of (B) is stereochemically enriched in certain stereoisomers. In some embodiments, the ascorbyl moiety of (B) is derived from D-ascorbic acid. In some embodiments, the ascorbyl moiety of (B) is derived from L-ascorbic acid. In some embodiments, the ascorbyl moiety of (B) is derived from L-ascorbic acid, and the R group in formula (I) is derived from palmitic acid, so that (B) is formula (Ia):

It is a compound of (Ia). Compounds of formula (Ia) are also known under any of the following names: 6-O-palmitoyl-L-ascorbic acid, L-ascorbic acid 6-hexadecanoate, L-ascorbyl palmitate, And ascorbic acid 6-palmitate.

(B) The ascorbyl carboxylate ester of formula (I) may be characterized as being substantially pure before being combined with the (A) prepolymer. “Substantially pure” (B) means 90 to 100 wt%, alternatively 95 to 100 wt%, alternatively 98 to 100 wt%, alternatively 90, of the total weight of (B), 95, or 98 to 99.99 wt%.

(B) Ascorbyl carboxylate ester of formula (I) uses a conventional esterification method and conditions to convert a 6-hydroxyl group (i.e., HOCH ₂ -) of ascorbic acid, and a carboxylate of formula RCO ₂ H Synthesized by coupling with an acid, a carboxylic anhydride of the formula RC(O)-OC(O)R, or an acid chloride of the formula RC(O)Cl, the compound of formula (I) and its corresponding carboxylic acid An ester group (ie, RC(O)-OCH ₂ -) can be provided.

(B) The ascorbyl carboxylate ester of formula (I) is 11.0 to 0.1 wt% of the total weight (100.00 wt%) of the combined weight of (A), (B), and optionally (C).

(B) The ascorbyl carboxylate ester of formula (I) is 11.0 to 0.05 wt%, alternatively 6.0 to 0.05 wt%, alternatively 3.0 to the total weight (100.00 wt%) of the moisture-curable agent. 0.10 wt%.

Ascorbic acid itself is (A) deactivated as a catalyst in moisture-curable formulations by the prepolymer, while (B) ascorbyl carboxylate esters later appear to be active. Formally, conversion of the 6-hydroxyl group of ascorbic acid itself to a carboxylic acid ester group unexpectedly provides an active catalyst of formula (I).

Without being bound by theory, it is believed that the selection of any specific R group in formula (I) of (B) does not have a complete neutralizing effect on the ability of (B) to catalyze the moisture curing of the moisture-curable agent. . Rather, it is thought that the choice of R mainly affects the solubility of (B) in the (A) prepolymer, where the greater the number of carbon atoms in R, the expected solubility of (B) in the (A) prepolymer (maximum load ) Becomes higher. In other words, by converting the 6-hydroxyl group in the ascorbic acid itself in the compound of formula (I) to a carboxylic ester group (i.e., RC(O)-OCH ₂ -), the resulting (B) in (A) The solubility of is substantially improved compared to the solubility of ascorbic acid itself in (A). Therefore, (A) loading of ascorbyl acetate (a compound of formula (I), wherein R is methyl) in the prepolymer is expected to be sufficient to achieve a technical solution.

Optional Constituent (C) Peroxide: A molecule containing a carbon atom, a hydrogen atom, and two or more oxygen atoms and having at least one -OO- group, or a collection of such molecules, provided that more than one -OO- group If present, each -OO- group is indirectly bonded to the other -OO- group through one or more carbon atoms. (C) the peroxide may be added to the moisture-curable formulation for curing, and the curing is performed by using the moisture-curable formulation comprising the constituents (A), (B), and (C) (C) the decomposition temperature of the peroxide or It includes heating to a higher temperature.

(C) The peroxide may be (C1) hydrocarbyl hydroperoxide. (C1) may be a compound of the formula R ^O -OOH, wherein R ^O is independently a (C ₁ -C ₂₀ )alkyl group or (C ₆ -C ₂₀ )aryl group. Each (C ₁ -C ₂₀ )alkyl group is independently unsubstituted or substituted with 1 or 2 (C ₆ -C ₁₂ )aryl groups. Each (C ₆ -C ₂₀ )aryl group is unsubstituted or substituted with 1 to 4 (C ₁ -C ₁₀ )alkyl groups. (C1) Hydroperoxide is 1,1-dimethylethyl hydroperoxide; 1,1-dimethylpropyl hydroperoxide; Benzoyl hydroperoxide; tert-butyl hydroperoxide; tert-amyl hydroperoxide; Or it may be cumyl hydroperoxide. Cumyl hydroperoxide is isopropylcumyl hydroperoxide; t-butylcumyl hydroperoxide; Or cumyl hydroperoxide; Alternatively it may be cumyl hydroperoxide (also known as cumene hydroperoxide, alpha,alpha-dimethylbenzyl hydroperoxide, CAS No. 80-15-9).

(C) The peroxide may be (C2) an organic peroxide. (C2) may be a single peroxide of the formula R ^O -OOR ^O , wherein each R ^O is independently as defined above. Alternatively, (C2) may be ^a diperoxide of the formula R ^O -OOR ^a -OOR ^O , wherein R ^a is a divalent hydrocarbon group, such as (C ₂ -C ₁₀ )alkylene, (C _3- C ₁₀ )cycloalkylene, or phenylene, and each R ^O is independently as defined above. (C2) the organic peroxide is bis(1,1-dimethylethyl) peroxide; Bis(1,1-dimethylpropyl) peroxide; 2,5-dimethyl-2,5-bis(1,1-dimethylethylperoxy) hexane; 2,5-dimethyl-2,5-bis(1,1-dimethylethylperoxy) hexine; 4,4-bis(1,1-dimethylethylperoxy) valeric acid; Butyl ester; 1,1-bis(1,1-dimethylethylperoxy)-3,3,5-trimethylcyclohexane; Benzoyl peroxide; tert-butyl peroxybenzoate; Di-tert-amyl peroxide (“DTAP”); Bis(alpha-t-butyl-peroxyisopropyl) benzene ("BIPB"); Isopropylcumyl t-butyl peroxide; t-butylcumyl peroxide; Di-t-butyl peroxide; 2,5-bis(t-butylperoxy)-2,5-dimethylhexane; 2,5-bis(t-butylperoxy)-2,5-dimethylhexine-3,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane; Isopropylcumyl cumylperoxide; Butyl 4,4-di(tert-butylperoxy) valerate; Or it may be di(isopropylcumyl) peroxide, or dicumyl peroxide. (C2) The organic peroxide may be dicumyl peroxide.

In some embodiments, only a blend of two or more (C) peroxides is used.

In some embodiments, at least one, alternatively each (C) peroxide contains one -O-O- group. In some embodiments, the moisture-curable formulation does not contain any (C) peroxide. In another embodiment, the moisture-curable agent comprises (C) peroxide, 0.01 to 4.5 wt%, alternatively 0.05 to 2 wt%, alternatively 0.10 to 2.0 wt%, alternatively 0.2 to 0.8 of the moisture-curable agent. It is contained in a concentration of wt%. When present in the moisture curable formulation, (C) peroxide is 0.01 to 1.0 wt%, alternatively 0.05 to 0.5 wt%, of the total weight (100.00 wt%) of the combined weight of (A), (B) and (C), Alternatively 0.08 to 0.20 wt%.

When the optional constituent (C) peroxide is used to prepare the moisture-curable agent, the moisture-curable agent is (C) peroxide and/or (B) of (C) peroxide-oxidation of ascorbyl carboxylate ester ( B ^Ox ) reaction products. (B) The reaction product of (C) peroxide-oxidation of (B ^Ox ) of ascorbyl carboxylate ester is in situ from the precursor form of a moisture-curable agent comprising (A), (B) and (C). Can be formed. Without being bound by theory, it is ^{believed that the} (B ^Ox ) reaction product is a more effective catalyst in catalyzing the moisture curing of the moisture-curable agent than the (B) ascorbyl carboxylate ester itself. That is, when (A) and (B) are included, but (C) is the first embodiment of the lacking moisture-curable formulation is divided into equal parts by weight, the first part by weight ((C) lacking) is the moisture curing condition Received as it is, and the second part by weight is further combined with the amount of (C) (for example, by soaking (C) in the second part by weight for 16 hours at 60° C.), (A), (B) and A second embodiment of a moisture-curable formulation comprising (C) is provided, wherein the second embodiment is subjected to the same moisture curing conditions, and the second embodiment of the moisture-curable formulation is a first embodiment of the moisture-curable formulation. It is expected to cure faster than the first part by weight of the form.

Optional Ingredients (Additives) (D) Flame retardant. (D) Flame retardants are compounds that inhibit or delay the spread of flames by inhibiting chemical reactions in the flame. In some embodiments, the (D) flame retardant is a compound that is (D1) a mineral, (D2) an organohalogen compound, (D3) (organic); (D4) silicon halide; Or (D5) a combination of any two or more of (D1) to (D4). Usually, halogenated (D) flame retardants are used with synergists to improve their efficacy. The synergist may be antimony trioxide. Examples of the halogen-free (D) flame retardant are inorganic minerals, organic nitrogen expandable compounds, and phosphorus-based expandable compounds. Examples of inorganic minerals are aluminum hydroxide and magnesium hydroxide. Examples of phosphorus-based expandable compounds include organic phosphonic acid, phosphonate, phosphinate, phosphonite, phosphinite, phosphine oxide, phosphine, phosphite, phosphate, phosphonitrilic chloride, phosphoric ester amide, phosphoric acid. Amides, phosphonic acid amides, phosphinic acid amides, melamine and melamine derivatives thereof (including melamine polyphosphate, melamine pyrophosphate and melamine cyanurate), and mixtures of two or more of these substances. Examples thereof include phenylbisdodecyl phosphate, phenylbisneopentyl phosphate, phenyl ethylene hydrogen phosphate, phenyl-bis-3,5,5' trimethylhexyl phosphate, ethyldiphenyl phosphate, 2-ethylhexyl di (p-tolyl ) Phosphate, diphenyl hydrogen phosphate, bis(2-ethyl-hexyl) para-tolylphosphate, tritolyl phosphate, bis(2-ethylhexyl)-phenyl phosphate, tri(nonylphenyl) phosphate, phenylmethyl hydrogen phosphate, Di(dodecyl) p-tolyl phosphate, tricresyl phosphate, triphenyl phosphate, triphenyl phosphate, dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl ) Phosphate, 2-ethylhexyldiphenyl phosphate and diphenyl hydrogen phosphate. Phosphoric acid esters of the type described in US Pat. No. 6,404,971 are examples of phosphorus-based flame retardants. Further examples include liquid phosphates such as bisphenol A diphosphate (BAPP) (Adeka Palmarole) and/or resorcinol bis (diphenyl phosphate) (Fyroflex RDP) (Supresta, ICI), ammonium polyphosphate (APP), pipette. Solid phosphorus such as ragine pyrophosphate and piperazine polyphosphate. Ammonium polyphosphates are often used with flame retardant auxiliary additives such as melamine derivatives. Melafine (DSM) (2,4,6-triamino-1,3,5-triazine; finely divided melamine) is also useful. In some embodiments, (D) is not present in the formulations and/or products of the present invention. In some embodiments, (D) is 0.1 to 20 wt %, alternatively 1 to 10 wt %, based on its total weight in the formulations and/or products of the present invention; And alternatively in a concentration of 5 to 20 wt %.

Optional Constituents (Additives) (E) Antioxidants: Organic molecules that inhibit oxidation, or a collection of these molecules. (E) Antioxidants function to provide antioxidant properties to moisture-curable agents and/or crosslinked polyolefin products. Examples of suitable (E) include bis(4-(1-methyl-1-phenylethyl)phenyl)amine (eg NAUGARD 445); 2,2'-methylene-bis(4-methyl-6-t-butylphenol) (eg VANOX MBPC); 2,2'-thiobis(2-t-butyl-5-methylphenol (CAS No. 90-66-4; 4,4'-thiobis(2-t-butyl-5-methylphenol)) (also 4 , Known as 4'-thiobis(6-tert-butyl-m-cresol), CAS No. 96-69-5, commercially LOWINOX TBM-6); 2,2'-thiobis(6-t- Butyl-4-methylphenol (CAS No. 90-66-4, commercially LOWINOX TBP-6); tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1, 3,5-triazine-2,4,6-trione (e.g. CYANOX 1790); pentaerythritol tetrakis (3-(3,5-bis(1,1-dimethylethyl)-4-hyde Roxyphenyl)propionate (e.g. IRGANOX 1010, CAS No. 6683-19-8); 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid 2,2'-T Odietandiyl ester (eg IRGANOX 1035, CAS number 41484-35-9); Distearyl thiodipropionate ("DSTDP"); Dilauryl thiodipropionate (eg IRGANOX PS 800 ); Stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (e.g. IRGANOX 1076); 2,4-bis(dodecylthiomethyl)-6-methyl Phenol (IRGANOX 1726); 4,6-bis(octylthiomethyl)-o-cresol (e.g. IRGANOX 1520); And 2',3-bis[[3-[3,5-di-tert-butyl -4-hydroxyphenyl]propionyl]] propionohydrazide (IRGANOX 1024). In some embodiments, (E) is 4,4'-thiobis(2-t-butyl-5-methylphenol) ( Also known as 4,4'-thiobis(6-tert-butyl-m-cresol); 2,2'-thiobis(6-t-butyl-4-methylphenol; tris[(4-tert-butyl- 3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazine-2,4,6-trione; distearyl thiodipropionate; or dilauryl thiodipropionate ; Or a combination of any two or more of these, wherein the combination is tris[(4-tert-butyl-3-hyde Oxy-2,6-dimethylethylphenyl)methyl]-1,3,5-triazine-2,4,6-trione and distearyl thiodipropionate. In some embodiments, the moisture-curable agent and/or the crosslinked polyolefin product does not comprise (E). If present, the (E) antioxidant may be 0.01 to 1.5 wt%, alternatively 0.05 to 1.2 wt%, alternatively 0.1 to 1.0 wt% of the total weight of the moisture-curable agent and/or crosslinked polyolefin product. have.

Optional Ingredients (Additives) (F) Metal deactivator. (F) The metal deactivating agent functions to chelate with transition metal ions (eg, the residue of the olefin polymerization catalyst) so that they are deactivated as an oxidation catalyst. Examples of (F) are N′1,N′12-bis(2-hydroxybenzoyl)dodecanedihydrazide (CAS No. 63245-38-5), and oxalyl bis(benzylidene hydrazide) (OABH )to be. In some embodiments, (F) is not present in the formulations and/or products of the present invention. In some embodiments, (F) is in a concentration of 0.001 to 0.2 wt%, alternatively 0.01 to 0.15 wt%, alternatively 0.01 to 0.10 wt%, all based on the total weight of the formulations and/or products of the invention. exist.

Optional Ingredients (Additives) (G) Colorants. For example, colorants or pigments. For example, carbon black or titanium dioxide. Carbon black is a poly(1-butene- co -ethylene) copolymer (more than 95% by weight to less than 100% by weight of the total weight of the master batch) and carbon black (more than 0% by weight to less than 5% by weight of the total weight of the master batch) It may be provided as a carbon black masterbatch that is a formulation of. Carbon black has a high surface area-to-volume ratio, but is a micro-divided form of paracrystalline carbon that is lower than activated carbon. Examples of carbon black are furnace carbon black, acetylene carbon black, conductive carbon (eg, carbon fiber, carbon nanotubes, graphene, graphite, and expanded graphite platelets). In some embodiments, (G) is not included in the formulations and/or products of the present invention. In some embodiments, (G) is present in the formulations and/or products of the present invention at a concentration of 0.1 to 35 wt %, alternatively 1 to 10 wt %, based on the total weight thereof.

Optional Ingredients (Additives) (H) Moisture remover. (H) The moisture scavenger functions to inhibit the premature moisture curing of the moisture-curable agent, and the early moisture curing will result from premature or prolonged exposure of the moisture-curable agent to the surrounding air. Examples of (H) are octyltriethoxysilane and octyltrimethoxysilane. In some embodiments, (H) is not included in the formulations and/or products of the present invention. In some embodiments, (H) is in a concentration of 0.001 to 0.2 wt%, alternatively 0.01 to 0.15 wt%, alternatively 0.01 to 0.10 wt%, all based on the total weight of the formulations and/or products of the invention. Exists as

Other optional ingredients. In some aspects, the formulations and products of the present invention do not contain any optional ingredients. In some embodiments, the formulations and products of the present invention do not contain any optional ingredients other than ingredients (C) to (H). In some embodiments, the formulations and/or products of the present invention are lubricants, mineral oils, anti-blocking agents, treeing retardants (water tree and/or electric tree retardants), coagents, It further contains a nucleating agent, a scorch retardant, a hindered amine light stabilizer, and at least one optional component (additive), which is a process aid.

Any optional ingredients may be useful to impart at least one characteristic or property to the formulations and/or products of the invention in which they are needed. The above features or characteristics may be useful for improving the performance of the formulations and/or products of the invention in operations or applications where the formulations and/or products of the invention are exposed to high operating temperatures. Such operations or applications include melt mixing, extrusion, shaping, hot water pipes, and insulating layers of power cables.

Any of the compounds herein includes all isotopic forms, including naturally occurring forms and/or isotopically enriched forms. The isotope-rich form may have additional uses, such as medical or anti-counterfeiting applications.

Unless otherwise indicated, the following applies. Alternatively, a separate embodiment precedes. ASTM stands for ASTM International, a standards organization based in West Conshohoken, Pennsylvania, USA. IEC stands for the International Electrotechnical Commission, a standards body based in Geneva, Switzerland. Any comparative examples are used for illustrative purposes only, and not prior art. Absence or lack is complete absence; Alternatively, it means it cannot be detected. IUPAC is the International Union of Pure and Applied Chemistry (IUPAC Secretariat, Research Triangle Park, North Carolina, USA). May is not something you must do, but giving you an allowed choice. By operable, we mean functionally possible or effective. Optionally means absent (or excluded), alternatively present (or included). PPM is based on weight. Properties are measured using standard test methods and measurement conditions (eg, viscosity at 23° C. and 101.3 kPa). Ranges include endpoints, subranges, and full and/or fractional values, except that integer ranges do not include fractional values. The room temperature is 23℃ ± 1℃. Substitution when referring to a compound is meant to include one or more substituents per substitution (including endpoints), instead of hydrogen.

Example

(Hydrolyzable silyl group)-functional prepolymer (A1): A reactor copolymer of 98.5 wt% of ethylene and 1.5 wt% of vinyltrimethoxysilane. Prepared by copolymerizing ethylene and vinyltrimethoxysilane in a tubular high pressure polyethylene reactor containing a free radical initiator. Available as SI-LINK™ DFDA-5451 from The Dow Chemical Company.

(Hydrolyzable silyl group)-functional polyolefin prepolymer (A2): 99.5 wt% of (hydrolyzable silyl group)-functional prepolymer (A1) plus 0.5 wt% of a moisture remover (H1) (hereinafter). Prepared by soaking a moisture remover (H1) in a (hydrolyzable silyl group)-functional prepolymer (A1).

Ascorbyl carboxylate ester (B1): ascorbyl palmitate. Available from Sigma-Aldrich Corporation, St. Louis, Missouri, USA

Constituent component (C1-1): cumyl hydroperoxide. Available as cumene hydroperoxide from Sigma-Aldrich Corporation.

Ascorbic acid ("AscrbA"): available from Sigma-Aldrich Corporation.

Methyl palmitate ("MePalm"): a compound of the formula CH ₃ (CH ₂ ) ₁₄ C(O)OCH ₃ . Available from Sigma-Aldrich Corporation.

Moisture-curable preparation sample preparation method: all the constituents used in any one of the formulations of Comparative Examples CE1 to CE8, and Inventive Examples IE1 to IE10 described below in Tables 1 and 2, if present, constituents (C1-1) Except for, by mixing at 40 rotations per minute (rpm) for 5 minutes at 145°C (target temperature about 20°C higher than the melting point of the prepolymer (A1)) in a batch type mixer, and components (A1) and (B1) , And it provides a moisture-curable formulation containing any of the other constituents shown in Tables 1 and 2 except that the constituent component (C1-1) is not included. After mixing, the sample is extruded into single strands at a temperature profile of 125° C. to 140° C., and the strands are pelleted in air to provide a comparative agent or a moisture-curable agent of the present invention in the form of pellets as appropriate. Constituents (C1-1), if used, are soaked into the pellets overnight at 60° C., and constituents (A), (B), and (C), and optionally any optional constituents shown in Table 2 It provides a moisture-curable formulation containing.

Plaque Preparation Test Method: The soaked pellets prepared by the moisture-curable preparation sample preparation method were compressed into plaques through a double compression process. The first compression was carried out at 120° C. under 3.45 megapascals (MPa, 500 psi) for 3 minutes, plus 172 MPa (25,000 psi) for 3 minutes. In the second step, the plaques were cut into squares, 3.45 MPa (500 psi) at 120° C. for 3 minutes, plus 180° C. to 185° C. for 15 minutes, or 210° C. to 215° C., both 172 MPa ( 25,000 psi), to give a second plaque having a thickness of 1.27 millimeters (mm, 50 mils).

High temperature creep test method. The degree of crosslinking in the test sample of the moisture-curable preparation prepared by the following moisture curing test method and the degree of curing accordingly are measured. High temperature creep measurements were performed at 150° C. with 20 Newtons per square centimeter (N/cm ² ), according to ICEA T-28-562. After 15 minutes, the maximum length under load was measured. Cool and measure the length of the test sample. The amount of elongation divided by the initial length gives a measure of hot creep as a percentage. The degree of elongation of the test sample is expressed as a percentage (%) of the length of the test sample after the high temperature creep condition to the initial length of the test sample before the high temperature creep condition. The lower the hot creep percentage, the lower the degree of elongation of the test sample under load, and thus the degree of crosslinking, and the greater the degree of hardening. The lower the high temperature creep value, the higher the degree of crosslinking implies.

Moisture hardening test method. Moisture cure and cure rate measurement test method. The second plaque was cured by immersing it in a water bath at 90° C. for 66 hours, and M _L (low torque value) at 182° C. was measured through a moving die rheometer (MDR). The torque of the test sample is measured using the following procedure. The test sample is heated at 180° C. for 20 minutes on a mobile die flow meter (MDR) instrument MDR2000 (Alpha Technologies), monitoring the change in torque to vibrational deformation of a 0.5 degree arc at 100 cpm. The minimum measured torque value is designated as "M _L ", and is expressed as a deciNewton-meter (dN-m). As curing or crosslinking proceeds, the measured torque value increases and eventually reaches the maximum torque value. The maximum or maximum measured torque value is designated as "M _H ", and is expressed as dN-m. When everything else is the same, the larger the M _H torque value, the greater the degree of crosslinking. When everything else is equal, the faster the torque value M _L reaches 1 pound-inch (1.1 dN-m), the faster the curing rate of the test sample. Conversely, the longer the torque value M _L needs to reach 1 pound-inch (1.1 dN-m), the slower the curing rate of the test sample. M _L represents the rheological change in the curing process, and the larger the value, the greater the degree of crosslinking. The cure time required to reach M _L = 1.0 lbf.in (1.1 decinewton-meters) was recorded.

Comparative Examples 1 to 8 (CE1 to CE8): Comparative formulations were prepared and tested by the method described above. Then refer to the results shown in Table 1.

Inventive Examples 1 to 10 (IE1 to IE10): The moisture-curable formulations of the present invention were prepared and tested by the method described above. Then refer to the results shown in Table 2.

In Tables 1 and 2, the time until reaching the torque value M _L = 1.1 dN-m indicates that the curing rate when using ascorbic acid as a catalyst in the comparative formulation is unacceptably slow. The cure rate when using ascorbyl palmitate in the moisture-curable formulation of the present invention is substantially faster.

High-temperature creep data in Tables 1 and 2 show that all of Inventive Examples IE2 to IE10 passed the high-temperature creep test, and one Inventive Example IE1 did not pass it, whereas all of Comparative Examples CE1 to CE8 did not pass the high-temperature creep test. Has shown that. This indicates that the moisture-curable formulation of the present invention can be cured into a moisture-cured polyolefin product, which advantageously has a higher degree of crosslinking than the comparative formulation. The lower the hot creep %, the greater the degree of crosslinking, and the greater the degree of crosslinking, the more suitable the moisture-cured polyolefin product is for use as a coating layer on power cables.

Claims (11)

As a moisture-curable formulation:
(A) (hydrolyzable silyl group)-functional polyolefin prepolymer; And
(B) Formula (I):

Including the ascorbyl carboxylate ester group of (I), wherein R is an unsubstituted (C ₁ -C ₄₅ )hydrocarbyl group;
(A) is 89.0 to 99.9 wt% (wt%) of the combined weight of (A) and (B), and (B) is 11.0 to 0.1 wt% of the combined weight of (A) and (B); And
The (A) is 40 to 99.9 wt% of the total weight of the moisture-curable formulation, (B) is 0.1 to 11 wt% of the total weight of the moisture-curable formulation, moisture-curable formulation. The method of claim 1, wherein the (A) (hydrolyzable silyl group)-functional polyolefin prepolymer is characterized by any one of restrictions (i) to (iii): (i) each hydrolyzable silyl group is independently a formula (II): (R ² ) _m (R ³ ) is a monovalent group of _3-m Si- (II); In the above formula, the subscript m is an integer of 1, 2, or 3; Each R ² is independently H, HO-, (C ₁ -C ₆ )alkoxy, (C ₂ -C ₆ )carboxy, ((C ₁ -C ₆ )alkyl) ₂ N-, (C ₁ -C ₆ )Alkyl(H)C=NO-, or ((C ₁ -C ₆ )alkyl) ₂ C=NO-; Each R ³ is independently (C ₁ -C ₆ )alkyl or phenyl; (ii) the polyolefin moiety of (A) is polyethylene-based, poly(ethylene- co- (C ₃ -C ₄₀ )alpha-olefin)-based, or a combination thereof; And (iii) a moisture-curable formulation, which is both (i) and (ii). The method according to claim 1 or 2, wherein the (B) ascorbyl carboxylate ester of formula (I) is characterized by any one of restrictions (i) to (xviii), wherein: (i) R is (C ₁ -C ₄₅ )alkyl group; (ii) R is a branched (C ₁ -C ₄₅ )alkyl group; (iii) R is a linear (C ₁ -C ₄₅ )alkyl group; (iv) R is an unsubstituted linear (C ₁ -C ₄₅ )alkyl group; (v) R is a (C ₁ -C ₃₅ )alkyl group; (vi) R is a (C ₁ -C ₂₅ )alkyl group; (vii) R is a (C ₉ -C ₂₅ )alkyl group; (viii) R is a (C ₁₁ -C ₁₉ )alkyl group; (ix) R is a (C ₁₂ -C ₁₈ )alkyl group; (x) R is a (C ₁₃ -C ₁₇ )alkyl group; (xi) R is a (C ₁₄ -C ₁₆ )alkyl group; (xii) R is a linear (C ₁₄ -C ₁₆ )alkyl group; (xiii) R is a (C ₁₄ )alkyl group; (xiv) R is a linear (C ₁₄ ) alkyl group; (xv) R is a (C ₁₅ )alkyl group; (xvi) R is a linear (C ₁₅ )alkyl group; (xvii) R is a (C ₁₆ )alkyl group; And (xviii) R is a straight chain (C ₁₆ ) alkyl group, a moisture-curable agent. The method according to claim 1 or 2, wherein the (B) ascorbyl carboxylate ester of formula (I) is characterized by any one of restrictions (i) to (v): (i) R is (C ₂ -C ₄₅ ) alkenyl group, (C ₆ -C ₁₂ ) aryl group, (C ₁ -C ₂₅ ) alkyl-substituted (C ₆ -C ₁₂ ) aryl group, or (C ₆ -C ₁₂ ) aryl-substituted Is a (C ₁ -C ₂₅ )alkyl group; (ii) R is a (C ₂ -C ₄₅ )alkenyl group; (iii) R is a (C ₆ -C ₁₂ )aryl group; (iv) R is a (C ₁ -C ₂₅ )alkyl-substituted (C ₆ -C ₁₂ )aryl group; And (v) R is a (C ₆ -C ₁₂ ) aryl-substituted (C ₁ -C ₂₅ ) alkyl group, a moisture-curable agent. The (B ^Ox ) reaction product of (B) oxidation of ascorbyl carboxylate ester with the (C) peroxide and/or the (C) peroxide according to any one of claims 1 to 4 is added. But include; The (C) peroxide is (C1) hydrocarbyl hydroperoxide or (C2) an organic peroxide, a moisture-curable preparation. The moisture-curable preparation according to any one of claims 1 to 5, further comprising at least one additive selected from additives (D) to (I): (D) a flame retardant; (E) antioxidants; (F) metal deactivating agents; (G) colorants; (H) moisture remover; And (I) a combination of any two or more of (D) to (H). As a method of preparing a moisture-curable preparation, the method comprises (A) (hydrolyzable silyl group)-functional polyolefin prepolymer and (B) formula (I):

Mixing the ascorbyl carboxylate ester of (I) to provide a mixture, wherein R is a (C ₁ -C ₄₅ )alkyl group; And melting or extruding the mixture to produce a moisture-curable formulation. In order to provide a moisture-cured polyolefin product, the moisture-curable agent according to any one of claims 1 to 6, or a product obtained by curing the moisture-curable agent prepared by the method of claim 7, moisture-curing Polyolefin product. An article of manufacture comprising a molded form of the moisture-cured polyolefin product of claim 8. A coated conductor comprising a conductive core and a polymer layer at least partially surrounding the conductive core, wherein at least a portion of the polymer layer comprises the moisture-cured polyolefin product of claim 8. A method of conducting electricity, the method comprising applying a voltage to a conductive core of the coated conductor of claim 10 to generate a flow of electricity through the conductive core.